Tetradentate and octahedral metal complexes containing naphthyridinocarbazole and its analogues
Tetradentate and octahedral metal complexes suitable for use as phosphorescent or delayed fluorescent and phosphorescent emitters in display and lighting applications.
1. A complex of Formula AII:
wherein:
M is Pt or Pd,
each of V 1 , V 2 , V 3 , and V 4 is coordinated with M,
V 1 and V 4 are N,
V 2 and V 3 are C,
each of L 1 and L 4 is independently substituted or unsubstituted pyridyl,
L 2 and L 3 is each independently substituted or unsubstituted phenyl,
each of A 1 , A 2 , A 3 , and A 4 is independently a single bond, CR 1 R 2 , C═O, SiR 1 R 2 , GeR 1 R 2 , NR 3 , PR 3 , R 3 P═O, AsR 3 , R 3 As═O, O, S, S═O, SO 2 , Se, Se═O, SeO 2 , BR 3 , R 3 Bi═O, or BiR 3 ,
each of X 1 and X 2 is N,
each of R a , R b , R c , and R d is independently present or absent, and if present each of R a , R b , R c , and R d is independently a mono-, di-, or tri-substitution as valency permits, and each of R a , R b , R c , and R d is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof, and
each of R x and R y is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination and
each of R 1 , R 2 and R 3 is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof.
2. The complex of claim 1 , wherein the complex has the structure of Formula AVII or Formula AVIII:
wherein:
M is Pt or Pd,
each of V 1 , V 2 , V 3 , and V 4 is coordinated with M,
each of V 1 and V 4 is N,
V 2 and V 3 are C,
each of L 1 and L 4 is independently substituted or unsubstituted pyridyl,
L 2 and L 3 is each independently substituted or unsubstituted phenyl,
each of A 1 , A 2 , A 3 , and A 4 is independently a single bond, CR 1 R 2 , C═O, SiR 1 R 2 , GeR 1 R 2 , NR 3 , PR 3 , R 3 P═O, AsR 3 , R 3 As═O, O, S, S═O, SO 2 , Se, Se═O, SeO 2 , BR 3 , R 3 Bi═O, or BiR 3 ,
X 1 is N,
X 2 is N,
X 3 is CR 1 , SiR 1 , GeR 1 , N, P, P═O, As, As═O, B, R 3 Bi═O or Bi,
each of R a , R b , R c , and R d is independently present or absent, and if present each of R a , R b , R c , and R d is independently a mono-, di-, or tri-substitution as valency permits, and each of R a , R b , R c , and R d is independently deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof, and
wherein each of R x , R y and R z is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination and
wherein each of R 1 , R 2 and R 3 is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof.
3. The complex of claim 1 , wherein the complex has a neutral charge.
4. A complex represented by one of the chemical structures in Structure 7, Structure 9, Structure 10, Structure 21, Structure 22, Structure 33, Structure 34, Structure 37, Structure 41, Structure 42, and Structure 45:
wherein each R, R 1 , R 2 , R 3 , and R 4 is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric, or any conjugate or combination thereof.
5. The complex of claim 1 , wherein
is one of the following structures:
wherein each of R 1 , R 2 , R 3 and R 4 is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof.
6. The complex of claim 1 , wherein each of the following structure:
7. The complex of claim 1 , wherein each of the following structure:
8. The complex of claim 1 , wherein each of
is the following structure:
9. The complex of claim 2 , wherein each of
independently one of the following structures:
wherein each of R, R 1 , and R 2 is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof.
10. An emitter comprising the complex of claim 4 .
11. An emitter comprising the complex of claim 1 , wherein the emitter is a delayed fluorescent and phosphorescent emitter.
12. An emitter comprising the complex of claim 1 , wherein the emitter is a phosphorescent emitter.
13. An emitter comprising the complex of claim 1 , wherein the emitter is a delayed fluorescent emitter.
14. The complex of claim 1 , wherein polymeric comprises polyalkylene, polyester, or polyether.
15. The complex of claim 14 , wherein polymeric comprises —(CH 2 O) n —CH 3 , —(CH 2 CH 2 O) n —CH 3 , —[CH 2 CH(CH 3 )] n —CH 3 , —[CH 2 CH(COOCH 3 )] n —CH 3 , —[CH 2 CH(COO CH 2 CH 3 )] n —CH 3 , or —[CH 2 CH(COO t Bu)] n —CH 3 , where n is an integer.
16. A device comprising a complex of claim 1 .